EP1632535A1 - Liquid formulations of direct dyes - Google Patents

Liquid formulations of direct dyes Download PDF

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Publication number
EP1632535A1
EP1632535A1 EP05016961A EP05016961A EP1632535A1 EP 1632535 A1 EP1632535 A1 EP 1632535A1 EP 05016961 A EP05016961 A EP 05016961A EP 05016961 A EP05016961 A EP 05016961A EP 1632535 A1 EP1632535 A1 EP 1632535A1
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EP
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Prior art keywords
direct
weight
dye
liquid formulation
aqueous liquid
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EP05016961A
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German (de)
French (fr)
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EP1632535B1 (en
Inventor
Gero Dr. Nordmann
Helmut Dr. Reichelt
Ingo Dr. Klopp
Gunter-Rudolf Dr. Schröder
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0072—Preparations with anionic dyes or reactive dyes
    • C09B67/0073—Preparations of acid or reactive dyes in liquid form
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/28—Colorants ; Pigments or opacifying agents

Definitions

  • brown dyes are required, which have a light brown, varying only in a narrow range hue.
  • the brown may be a dye mixture which is based on the synthesis, as in the case of Basic Brown 1, or a dye mixture of a yellow dye, a blue dye and optionally a red dye.
  • Dye mixtures have the great advantage that a nuance of the color is easier. However, it is problematic to obtain storage-stable liquid formulations of these dye mixtures.
  • solubility-enhancing additives are generally selected, which often serve as a counterion of the dye acids.
  • solubility-improving additives the most diverse classes of substances are known, such as alcohols, mono-, oligo- or polyalkylene glycols, lactams, amines and amides.
  • EP-A-1 258 562 describes blends of Direct Yellow 11 and Direct Orange 15 which, however, do not contain any solubility-improving additives.
  • the earlier European application 3 029 578 teaches storage-stable liquid formulations of reddened Direct Yellow 11 by adding a mixture of urea and ethanolamine.
  • Low molecular weight polyvinylformamide and its hydrolysis product polyvinylamine are fixing agents in papermaking.
  • the cationic charge of the polyvinylamine brings about a bond between anionic dyes and the weakly anionically charged paper fibers and thus fixes the dyes added to the aqueous paper stock in the dyeing process on the paper fiber.
  • EP-A-663 031 teaches the addition of polyvinylformamide different degrees of hydrolyzation as a fixing agent in the dyeing in the mass during the papermaking process.
  • JP 01 024 873 describes recording fluids containing poly-N-vinylformamide. However, these recording liquids do not contain a dye composition with Direct Yellow 11.
  • the storage stability of the brown aqueous liquid formulations was the object of the present invention. Since the brown liquid formulation is prepared from a yellow / orange liquid formulation that is tinted with red and blue, the yellow / orange liquid formulation must also have a long shelf life. In addition, the auxiliaries added to the yellow / orange liquid formulation must also have a stabilizing effect in the brown liquid formulation, since their separation would not be practicable.
  • the present invention was thus based on a liquid formulation which has improved storage stability for both the yellow / orange dye and the brown dye composition both in cold and in warm storage.
  • the aqueous liquid formulation comprises poly-N-vinylformamide and / or a polymer obtained by polymerizing a mixture of one or more ethylenically unsaturated monomers and> 50% by weight of N-vinylformamide based on the total monomers.
  • Poly-N-vinylformamide is a polymer having an average molecular weight in the range of ⁇ 340,000. The average molecular weight was determined by stat. Light scattering determined. Preference is given to a poly-N-vinylformamide whose average molecular weight is in the range from 300 to 100,000, in particular from 300 to 10,000. Poly-N-vinylformamide is well known. It is obtained by polymerization of vinylformamide. Its preparation is described for example in DE-A-312 84 78.
  • N-vinylformamide is carried out by known methods using radical polymerization initiators such as peroxides, hydroperoxides, redox catalysts or radical-decomposing azo compounds.
  • the polymerization is carried out in a solvent or diluent in a temperature range of 30 to 140 ° C.
  • polymers of a different molecular weight are obtained which can be characterized by means of the Fikentscher K values.
  • the K value can vary within a wide range between 10 and 200.
  • Polymers having a high K value, eg, above 80, are preferably prepared by polymerizing the N-vinylformamide in water.
  • Polymers of a lower K value are obtained by carrying out the polymerization in the presence of known polymerization regulators or in a solvent which controls the polymerization, for example alcohols, such as methanol, ethanol, n- and isopropanol, and acetone and methyl ethyl ketone.
  • Other polymerization regulators are, for example, hydroxylammonium salts, chlorinated hydrocarbons and thio compounds, such as dodecylmercaptan.
  • lower K polymers can be obtained by using azo compound based polymerization initiators soluble therein.
  • a particularly suitable azo compound for the polymerization in isopropanol is, for example, 2,2'-azobis (isobutyronitrile).
  • water-soluble azo compounds such as 2,2'-azobis (2-amidinopropane) hydrochloride and 4,4'-azobis (4'-cyanopentanoic acid), wherein the reaction in aqueous solution.
  • the polymerization can be carried out in the manner of a water-in-oil emulsion polymerization.
  • the reverse suspension polymerization for the preparation of finely divided polymers is possible.
  • the pH in the polymerization - if it is carried out in an aqueous medium - is in the range of 4 to 9.
  • polymer solutions are mainly prepared whose solids content is 5 to 50 wt .-%.
  • polyvinylformamide is therefore to be understood as meaning a polymer which contains up to 20 mol% of hydrolyzed groups.
  • the degree of hydrolysis can be easily determined by polyelectrolyte titration.
  • a degree of hydrolysis is preferably ⁇ 15 mol%, in particular ⁇ 10 mol%, very particularly preferably ⁇ 5 mol%.
  • ethylenically unsaturated comonomers are vinyl formate, vinyl acetate, vinyl propionate, acrylonitrile, N-vinylcaprolactam, N-vinylurea, N-vinylpyrrolidone, C 1 -C 6 -alkyl vinyl ethers, N-vinylacetamide, methyl acrylate and methyl methacrylate.
  • aqueous liquid formulations comprising 5-25% by weight of the dye composition and 1-25% by weight, in particular 1-15% by weight, of poly-N-vinylformamide, based on the total weight of the liquid formulation.
  • the percentages by weight of the dyes in each case refer to the dye calculated in the form of its free acid.
  • the dyes are present in the liquid formulation in the form of their salts.
  • the dyes obtained by reacting Direct Yellow 11 preferably have as counterions alkali ions such as sodium, potassium and in particular lithium ions.
  • Direct Yellow 11 and Direct Orange 15 are stilbene dyes.
  • Direct Yellow 11 is obtained as a product of the self-condensation of 5-nitro-o-toluenesulfonic acid in an aqueous alkaline medium. Its reaction with reducing agents such as glucose or sodium sulfide leads to Direct Orange 15 (C.I. 40002 or 40003). These dyes are mixtures of dyes of indeterminate constitution.
  • Direct Orange 15 is understood by the person skilled in the art to be mixtures whose hue angle according to CIELAB on bleached pulp varies in the color space in the range from 45 to ⁇ 55.
  • reddening of Direct Yellow 11.
  • Such reddening of hue can also be achieved by thermal treatment of Direct Yellow 11 at a pH in the range of 12-13.
  • Yellow-orange dyes hereinafter also referred to as partially reddened dyes, which are obtainable by reduction or thermal treatment of Direct Yellow 11 and its hue angle on bleached pulp in the color space in the range from 55 to 75, in particular in the range from 55 to 65, are preferred.
  • direct blue dyes are meant direct dyes having an absorption maximum in the wavelength range from 560 to 650 nm.
  • Red direct dyes are to be understood as meaning direct dyes having an absorption maximum in the wavelength range from 490 to 540.
  • blue direct dyes such as Direct Violet 9 (CI 27855), Direct Violet 35, Direct Violet 51 (CI 27905), Direct Blue 86 (CI 74180), Direct Blue 199 (CI 74190), Direct Blue 218 (CI 24401), Direct Blue 267, Direct Blue 273, Direct Blue 279, Direct Blue 281, Direct Blue 71, 273 as a copper complex, and 290.
  • Direct Blue 15, 279, 281, 290 and the dyes of Formulas I, II and III are preferred.
  • red direct dyes such as Direct Red 80, Direct Red 81 (C.I. 28160), Direct Red 239, Direct Red 252-255 and Direct Red 262.
  • a brown direct dye preferably Direct Brown 44
  • a red dye is used in this case.
  • orange dyes are Direct Orange 15, Direct Orange 34 (C.I. 40215) and Direct Orange 102 (C.I., 29156). In general, however, this will not be done, as can be achieved with the partially reddened dyes and optionally the red or the brown direct dye all nuances.
  • Reddening of Direct Yellow 11 is achieved, for example, by its reaction with formaldehyde or by basic condensation of 5-nitrotoluenesulphonic acid in the presence of formaldehyde. Furthermore, a scorching is achieved by the addition of glucose or sodium sulfide. Further redness reactions are reported in the Color Index and in the literature cited therein C.I. 40001, 40002, 40003.
  • Organic reducing agents are, for example, hydroxyaldehydes such as pentoses, hexoses and heptoses, preferably glucose.
  • the preferred partially reddened dyes are obtainable by substoichiometric reduction based on the nitrotoluenesulfonic acid.
  • Particularly preferred partially reddened dyes are obtained by reacting Direct Yellow 11 with 0.05 to 0.3 mol, preferably 0.1 to 0.25 mol, of hydroxyaldehyde, in particular glucose, per mole of nitrotoluenesulfonic acid used.
  • the reddening reaction can be stopped by neutralizing and cooling.
  • Direct Yellow 11 is well known. Direct Yellow 11 is obtained by heating an alkaline aqueous solution of nitrotoluenesulfonic acid. The reaction of nitrotoluenesulphonic acid with an alkali metal hydroxide, such as sodium hydroxide or, preferably, lithium hydroxide, first forms the salt of nitrotoluenesulphonic acid, which condenses to the azo-styrenic dye in the base when heated to 40.degree.-80.degree.
  • an alkali metal hydroxide such as sodium hydroxide or, preferably, lithium hydroxide
  • Alkanolamines are, for example, ethanolamine, isopropanolamine or preferably diethanolamine. Presumably, such an additive acts solubilizing reaction intermediates.
  • the alkaline mixture is made neutral approximately neutral, for example, with acetic acid.
  • neutral points are to be understood as meaning pH values in the range from 7 to 9.
  • a direct yellow 11 is used to prepare the partially reddened or reddened dyestuff, which is obtainable by reacting 1 mol of nitrotoluenesulphonic acid with 1.4 to 1.8 mol of lithium hydroxide, adding from 0.1 to 0.5 mol of alkanolamine , Heating the reaction mixture to 40 to 80 ° C and neutral.
  • the preparation of Direct Yellow 11 and the Verrötungs technically be carried out without intermediate isolation of Direct Yellow 11.
  • the partially reddened dye is then directly obtainable by reacting 1 mol of nitrotoluenesulfonic acid with 1.4 to 1.8 mol of lithium hydroxide, adding 0.1 to 0.5 mol of alkanolamine, heating the reaction mixture to 40 to 80 ° C, reacting with 0, 05 to 0.3 moles of glucose based on one mole of nitrotoluenesulfonic acid used and neutral points.
  • Particularly preferred is a procedure in which during the coupling and reduction, the temperature is increased continuously, in a linear or non-linear manner, or periodically.
  • the temperature difference between the beginning of the coupling and the end of the reduction can be up to 40 K. In general, this difference is 15 to 25 K.
  • Mixtures are preferred in which the sum of the two components is 10-25% by weight. That is, at low Polyvinylformamidgehalt in the range of 1 - 5 wt .-%, high urea contents in the range of> 9-24 wt .-% are preferred. If only 1-9% by weight of urea is added, the preferred proportion of polyvinylformamide is> 5-16% by weight.
  • aqueous liquid formulations comprising 10-25% by weight of dye composition, 1-15% by weight of poly-N-vinylformamide and 1-30% by weight of urea. Particular preference is given to aqueous liquid formulations comprising 15-20% by weight of dye composition, especially the preferred dye compositions, 1-10% by weight of poly-N-vinylformamide and 1-20% by weight of urea.
  • liquid formulations comprising 5-25% by weight of the dye composition, 1-15% by weight, preferably 1-10% by weight of poly-N-vinylformamide, 0.5-5% by weight, preferably 1.5-3% by weight of an alkanolamine and 1-30% by weight. %, preferably 1-25 wt.%, Urea preferred.
  • the dyes can be used as a moist presscake or in a dried form.
  • a solution is prepared by adding the poly-N-vinylformamide and the urea. Preference is given to directly using the reaction mixture of the reddening reaction of Direct Yellow 11 without additional isolation steps.
  • the urea of the reaction mixture obtained is first added to the reddening reaction of Direct Yellow 11. Subsequently, the poly-N-vinylformamide and optionally the further dyes are added.
  • additives in the liquid formulation may in principle be C 1 -C 4 -alkanols, for example methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol or tert-butanol, carboxamides, such as N, N-dimethylformamide or N, N Dimethylacetamide, ketones or ketoalcohols such as acetone, methyl ethyl ketone or 2-methyl-2-hydroxypentan-4-one, mono-, oligo- or polyalkylene glycols or thioglycols having C 2 -C 6 -alkylene units such as ethylene glycol, 1,2 or 1,3-propylene glycol, 1,2- or 1,4-butylene glycol, hexane-1,6-diol, diethylene glycol, triethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol or polypropylene glycol, other
  • Suitable solubilizing additives are also lactams, such as ⁇ -caprolactam, pyrrolidin-2-one or N-methylpyrrolidin-2-one, cyclic ureas, such as 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimid-2-one and Polyacrylic acids, polyacrylic acid derivatives, polyvinyl acetates, polyvinyl alcohols, polyvinylpyrrolidones, polysiloxanes or copolymers of the respective monomers. Likewise, oligomers of ethylene oxide or propylene oxide or derivatives of these oligomers may be used.
  • liquid formulations of the present invention contain no (i.e., ⁇ 1% by weight) such additives.
  • liquid formulations with Direct Brown 44 additionally contain up to 5% by weight of polyethylene glycol as additive.
  • the solutions obtained have excellent storage stability. They give good paper coloration especially in the mass.
  • Example 1 liquid formulations with compositions to be taken from Table 1 were prepared.
  • Table 2 represents the selected dye compositions.
  • the yellow dye used in Examples 1-9 and Comparative Examples V1 and V2 was the reddish Direct Yellow 11 (dye content 26.2% by weight) prepared according to a) and the one prepared according to b) in Examples 10, 11 and V3 Reddened Direct Yellow 11 (dye content 25.0% used.
  • Table 1 Ex. urea Polyvinylformamide * H 2 O Farbstoffzus. Stability n.
  • DR 239 is added as a concentrated aqueous solution of the mixed sodium / ethanolammonium salt, DR 81 as a concentrated aqueous solution of the triethanolammonium salt, D.Bn. 44 as a concentrated aqueous solution of the mixed sodium / ammonium salt the amount of colored acid is given, DB 279 is added as a concentrated aqueous solution of the triethanolammonium salt, DB 281 as a concentrated aqueous solution of the mixed sodium / lithium salt.

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Abstract

An aqueous liquid formulation comprises (wt.%): dye composition (5 - 25) containing Direct yellow 11, or dye obtained by reduction or thermal treatment of Direct yellow 11 (20 - 100), blue direct dye (0 - 30), red direct dye (0 - 30) and brown direct dye (0 - 60); and poly-N-vinylformamide and/or polymer obtained by polymerization of ethylenically unsaturated monomer(s) and N-vinylformamide (greater than 50 of the monomers) (1 - 25).

Description

Die vorliegende Erfindung betrifft wässrige Flüssigformulierungen enthaltend

5-25 Gew.-%
einer Farbstoffzusammensetzung umfassend
20-100 Gew.-% Direct Yellow 11 oder eines Farbstoffs erhältlich durch Reduktion oder thermische Behandlung von Direct Yellow 11
0-30 Gew.-% eines blauen Direktfarbstoffes,
0-30 Gew.-% eines roten Direktfarbstoffes und
0-60 Gew.-% eines braunen Direktfarbstoffes jeweils bezogen auf die Farbstoffzusammensetzung und
1-25 Gew.-%
Poly-N-vinylformamid und/oder eines Polymers, das erhalten wird durch Polymerisation einer Mischung aus einem oder mehreren ethylenisch ungesättigten Monomere und > 50 Gew.-% N-Vinylformamid bezogen auf die Gesamtmonomere,
bezogen auf das Gesamtgewicht der wässrigen Flüssigformulierung, sowie ihre Verwendung zum Färben von Cellulosematerial insbesondere Papier.The present invention relates to aqueous liquid formulations containing
5-25% by weight
a dye composition comprising
20-100% by weight of Direct Yellow 11 or a dye obtainable by reduction or thermal treatment of Direct Yellow 11
0-30% by weight of a blue direct dye,
0-30 wt .-% of a red direct dye and
0-60 wt .-% of a brown direct dye in each case based on the dye composition and
1-25% by weight
Poly-N-vinylformamide and / or a polymer obtained by polymerizing a mixture of one or more ethylenically unsaturated monomers and> 50% by weight of N-vinylformamide based on the total monomers,
based on the total weight of the aqueous liquid formulation, and their use for dyeing cellulosic material, in particular paper.

Für die Herstellung von Verpackungsmaterial werden Braunfarbstoffe benötigt, die einen hellbraunen, nur in einem engen Bereich variierenden Farbton aufweisen. Das Braun kann dabei ein synthesebedingtes Farbstoffgemisch sein, wie im Fall von Basic Brown 1, oder eine Farbstoffmischung aus einem Gelbfarbstoff, einem Blaufarbstoff und gegebenenfalls einem Rotfarbstoff. Farbstoffmischungen haben den großen Vorteil, dass eine Nuancierung des Farbtons leichter möglich ist. Problematisch ist es jedoch, lagerstabile Flüssigformulierungen dieser Farbstoffmischungen zu erhalten.For the production of packaging material brown dyes are required, which have a light brown, varying only in a narrow range hue. The brown may be a dye mixture which is based on the synthesis, as in the case of Basic Brown 1, or a dye mixture of a yellow dye, a blue dye and optionally a red dye. Dye mixtures have the great advantage that a nuance of the color is easier. However, it is problematic to obtain storage-stable liquid formulations of these dye mixtures.

Schlechte Lagerstabilität von Flüssigformulierungen resultiert aus der oftmals begrenzten Löslichkeit der Farbstoffe in Wasser, da diese wiederum meist mit einer erwünschten hohen Affinität zur Faser einhergeht. Während dies für die in der Papiermaschine vorliegenden Farbstoffkonzentrationen aufgrund der niedrigen Konzentration keine Auswirkung hat, kann es für die im Handel immer beliebteren Flüssigformulierungen große Auswirkungen haben. Oftmals ergeben sich Probleme mit der Lagerstabilität der Flüssigformulierung, wenn die Fässer längere Zeit gelagert werden müssen. Dabei können sowohl Kälte wie auch Hitze zu Niederschlägen führen, die nicht nur kritisch für die Dosierpumpen sein können sondern auch zur Stippenbildung oder ungleichmäßigen Färbungen des Papiers führen können. Noch problematischer wird die Lagerstabilität bei Farbstoffmischungen, da hier mehrere Farbstoffe gleichzeitig in Lösung gehalten werden müssen.Poor storage stability of liquid formulations results from the often limited solubility of the dyes in water, as this in turn is usually associated with a desired high affinity for the fiber. While this has no effect on the levels of dye present in the paper machine due to the low concentration, it may have a major impact on the more popular liquid formulations in the trade. Often there are problems with the storage stability of the liquid formulation when the barrels have to be stored for a long time. Both cold and heat can lead to precipitation, which can not only be critical for the metering pumps but can also lead to specks or uneven dyeings of the paper. Even more problematic is the storage stability in dye mixtures, since several dyes must be kept in solution at the same time.

Um generell die Löslichkeit einer Farbstoffformulierung zu verbessern, werden in der Regel löslichkeitsverbessernde Zusätze gewählt, die oftmals auch als Gegenion der Farbstoffsäuren dienen. Als löslichkeitsverbessernde Zusätze sind die verschiedensten Stoffklassen bekannt wie Alkohole, Mono-, Oligo- oder Polyalkylenglykole, Lactame, Amine und Amide.To generally improve the solubility of a dye formulation, solubility-enhancing additives are generally selected, which often serve as a counterion of the dye acids. As solubility-improving additives, the most diverse classes of substances are known, such as alcohols, mono-, oligo- or polyalkylene glycols, lactams, amines and amides.

Die EP-A-1 258 562 beschreibt Braunmischungen mit Direct Yellow 11 sowie mit Direct Orange 15, die jedoch keinerlei löslichkeitsverbessernde Zusätze enthalten.EP-A-1 258 562 describes blends of Direct Yellow 11 and Direct Orange 15 which, however, do not contain any solubility-improving additives.

Die ältere europäische Anmeldung 3 029 578 lehrt lagerstabile Flüssigformulierungen von verrötetem Direct Yellow 11 durch Zusatz einer Mischung aus Harnstoff und Ethanolamin.The earlier European application 3 029 578 teaches storage-stable liquid formulations of reddened Direct Yellow 11 by adding a mixture of urea and ethanolamine.

Niedermolekulares Polyvinylformamid sowie dessen Hydrolyseprodukt Polyvinylamin sind Fixiermittel bei der Papierherstellung. Die kationische Ladung des Polyvinylamins bewirkt eine Bindung zwischen anionischen Farbstoffen und den schwach anionisch geladenen Papierfasern und fixiert so die im Färbeprozess dem wässrigen Papierstoff zugesetzten Farbstoffe auf der Papierfaser. So lehrt die EP-A-663 031 den Zusatz von Polyvinylformamid unterschiedlichen Hydrolysierungsgrades als Fixiermittel beim Färben in der Masse während des Papierherstellungsprozesses.Low molecular weight polyvinylformamide and its hydrolysis product polyvinylamine are fixing agents in papermaking. The cationic charge of the polyvinylamine brings about a bond between anionic dyes and the weakly anionically charged paper fibers and thus fixes the dyes added to the aqueous paper stock in the dyeing process on the paper fiber. Thus, EP-A-663 031 teaches the addition of polyvinylformamide different degrees of hydrolyzation as a fixing agent in the dyeing in the mass during the papermaking process.

Die JP 01 024 873 beschreibt Aufzeichnungsflüssigkeiten enthaltend Poly-N-vinylformamid. Diese Aufzeichnungsflüssigkeiten enthalten jedoch keine Farbstoffzusammensetzung mit Direct Yellow 11.JP 01 024 873 describes recording fluids containing poly-N-vinylformamide. However, these recording liquids do not contain a dye composition with Direct Yellow 11.

Für die Herstellung von Verpackungsmaterial war es nun das Ziel, dem jeweiligen Papierhersteller speziell für seinen Rohzellstoff fertig abgemischte Braunmischungen anzubieten. Das hat für ihn den Vorteil, dass er zum einen nicht selber mischen muss und zum anderen nur noch die eine Braunfarbstoffmischung lagern muss. Damit wurde die Lagerstabilität der braunen wässrigen Flüssigformulierungen zur Aufgabe der vorliegenden Erfindung. Da die braune Flüssigformulierung ausgehend von einer gelb/orangen Flüssigformulierung hergestellt wird, die mit Rot und Blau abgetönt wird, muss auch die gelb/orange Flüssigformulierung eine hohe Lagerstabilität aufweisen. Darüber hinaus müssen die der gelb/orangen Flüssigformulierung zugesetzten Hilfsmittel auch in der braunen Flüssigformulierung stabilisierend wirken, da ihre Abtrennung nicht praktikabel wäre.For the production of packaging material, the aim now was to offer the respective paper manufacturer specially blended blends for his raw pulp. This has the advantage for him that he does not have to mix for his part and that he only has to store one brown dye mixture. Thus, the storage stability of the brown aqueous liquid formulations was the object of the present invention. Since the brown liquid formulation is prepared from a yellow / orange liquid formulation that is tinted with red and blue, the yellow / orange liquid formulation must also have a long shelf life. In addition, the auxiliaries added to the yellow / orange liquid formulation must also have a stabilizing effect in the brown liquid formulation, since their separation would not be practicable.

Der vorliegenden Erfindung lag somit eine Flüssigformulierung als Aufgabe zugrunde, die für sowohl den gelb/orangen Farbstoff wie auch für die braune Farbstoffzusammensetzung eine verbesserte Lagerstabilität sowohl bei kalter wie auch bei warmer Lagerung aufweist.The present invention was thus based on a liquid formulation which has improved storage stability for both the yellow / orange dye and the brown dye composition both in cold and in warm storage.

Demgemäss wurden die obengenannten Flüssigformulierungen gefunden.Accordingly, the above liquid formulations were found.

Erfindungsgemäß enthält die wässrige Flüssigformulierung Poly-N-vinylformamid und/oder ein Polymer, das erhalten wird durch Polymerisation einer Mischung aus einem oder mehreren ethylenisch ungesättigten Monomere und > 50 Gew.-% N-Vinylformamid bezogen auf die Gesamtmonomere.According to the invention, the aqueous liquid formulation comprises poly-N-vinylformamide and / or a polymer obtained by polymerizing a mixture of one or more ethylenically unsaturated monomers and> 50% by weight of N-vinylformamide based on the total monomers.

Poly-N-vinylformamid ist ein Polymer mit einem mittleren Molekulargewicht im Bereich von ≤ 340 000. Das mittlere Molekulargewicht wurde mittels stat. Lichtstreuung bestimmt. Bevorzugt wird ein Poly-N-vinylformamid dessen mittleres Molekulargewicht im Bereich von 300 -100 000 insbesondere von 300 bis 10 000 liegt. Poly-N-vinylformamid ist allgemein bekannt. Man erhält es durch Polymerisation von Vinylformamid. Seine Herstellung wird beispielsweise in der DE-A-312 84 78 beschrieben.Poly-N-vinylformamide is a polymer having an average molecular weight in the range of ≦ 340,000. The average molecular weight was determined by stat. Light scattering determined. Preference is given to a poly-N-vinylformamide whose average molecular weight is in the range from 300 to 100,000, in particular from 300 to 10,000. Poly-N-vinylformamide is well known. It is obtained by polymerization of vinylformamide. Its preparation is described for example in DE-A-312 84 78.

Die Polymerisation von N-Vinylformamid erfolgt nach bekannten Verfahren unter Verwendung radikalischer Polymerisationsinitiatoren, wie Peroxiden, Hydroperoxiden, Redoxkatalysatoren oder von in Radikale zerfallenden Azoverbindungen. Die Polymerisation wird in einem Lösungs- bzw. Verdünnungsmittel in einem Temperaturbereich von 30 bis 140°C durchgeführt. In Abhängigkeit von den Polymerisationsbedingungen erhält man Polymerisate eines unterschiedlichen Molekulargewichts, das mit Hilfe der K-Werte nach Fikentscher charakterisiert werden kann. Der K-Wert kann in einem weiten Bereich zwischen 10 und 200 schwanken. Polymerisate mit einem hohen K-Wert, z.B. von oberhalb 80, werden vorzugsweise durch Polymerisieren des N-Vinylformamids in Wasser hergestellt. Polymerisate eines niedrigeren K-Wertes, z.B. unterhalb von 80, erhält man, wenn man die Polymerisation in Gegenwart von bekannten Polymerisationsreglern oder in einem Lösungsmittel durchführt, das die Polymerisation regelt, z.B. Alkohole, wie Methanol, Ethanol, n- und Isopropanol, sowie Aceton und Methylethylketon. Andere Polymerisationsregler sind beispielsweise Hydroxylammoniumsalze, chlorierte Kohlenwasserstoffe und Thioverbindungen, wie Dodecylmercaptan. Polymerisate eines niedrigeren K-Wertes können z.B. durch Verwendung von darin löslichen Polymerisationsinitiatoren auf Basis von Azoverbindungen erhalten werden. Eine besonders geeignete Azoverbindung für die Polymerisation in Isopropanol ist beispielsweise 2,2'-Azo-bis-(isobutyronitril). Für die Herstellung hochmolekularer Polymerisate des N-vinylformamids verwendet man wasserlösliche Azoverbindungen, z.B. 2,2'-Azobis(2-amidinopropan)-hydrochlorid und 4,4'-Azobis-(4'-cyan-pentansäure), wobei man die Reaktion in wässriger Lösung durchführt. Außer einer Lösungspolymerisation in Wasser, einem in Wasser löslichen Lösungsmittel, Mischungen aus Wasser und einem in Wasser löslichen Lösungsmittel kann die Polymerisation nach Art einer Wasser-in-Öl-Emulsionspolymerisation erfolgen. Auch die umgekehrte Suspensionspolymerisation zur Herstellung feinteiliger Polymerisate ist möglich. Der pH-Wert bei der Polymerisation - sofern in einem wässrigen Medium gearbeitet wird - liegt in dem Bereich von 4 bis 9. Bei der Lösungspolymerisation werden vorwiegend Polymerisatlösungen herstellt, deren Feststoffgehalt 5 bis 50 Gew.-% beträgt.The polymerization of N-vinylformamide is carried out by known methods using radical polymerization initiators such as peroxides, hydroperoxides, redox catalysts or radical-decomposing azo compounds. The polymerization is carried out in a solvent or diluent in a temperature range of 30 to 140 ° C. Depending on the polymerization conditions, polymers of a different molecular weight are obtained which can be characterized by means of the Fikentscher K values. The K value can vary within a wide range between 10 and 200. Polymers having a high K value, eg, above 80, are preferably prepared by polymerizing the N-vinylformamide in water. Polymers of a lower K value, for example below 80, are obtained by carrying out the polymerization in the presence of known polymerization regulators or in a solvent which controls the polymerization, for example alcohols, such as methanol, ethanol, n- and isopropanol, and acetone and methyl ethyl ketone. Other polymerization regulators are, for example, hydroxylammonium salts, chlorinated hydrocarbons and thio compounds, such as dodecylmercaptan. For example, lower K polymers can be obtained by using azo compound based polymerization initiators soluble therein. A particularly suitable azo compound for the polymerization in isopropanol is, for example, 2,2'-azobis (isobutyronitrile). For the preparation of high molecular weight polymers of N-vinylformamide used water-soluble azo compounds, such as 2,2'-azobis (2-amidinopropane) hydrochloride and 4,4'-azobis (4'-cyanopentanoic acid), wherein the reaction in aqueous solution. In addition to a solution polymerization in water, a water-soluble solvent, mixtures of water and a water-soluble solvent, the polymerization can be carried out in the manner of a water-in-oil emulsion polymerization. The reverse suspension polymerization for the preparation of finely divided polymers is possible. The pH in the polymerization - if it is carried out in an aqueous medium - is in the range of 4 to 9. In the solution polymerization polymer solutions are mainly prepared whose solids content is 5 to 50 wt .-%.

Bedingt durch seine Herstellung sowie durch die wässrige Flüssigformulierung lässt sich die Hydrolyse der Amidgruppe zur Amingruppe nicht vollständig vermeiden. Unter Polyvinylformamid ist daher im Rahmen dieser Anmeldung ein Polymer zu verstehen, das bis zu 20 Mol-% hydrolysierte Gruppen enthält. Der Hydrolysegrad lässt sich einfach mittels Polyelektrolyttitration bestimmen. Bevorzugt ist ein Hydrolysegrad ≤ 15 Mol-%, insbesondere ≤ 10 Mol-%, ganz besonders bevorzugt ≤ 5 Mol-%.Due to its preparation and the aqueous liquid formulation, the hydrolysis of the amide group to the amine group can not be completely avoided. For the purposes of this application, polyvinylformamide is therefore to be understood as meaning a polymer which contains up to 20 mol% of hydrolyzed groups. The degree of hydrolysis can be easily determined by polyelectrolyte titration. A degree of hydrolysis is preferably ≦ 15 mol%, in particular ≦ 10 mol%, very particularly preferably ≦ 5 mol%.

Als ethylenisch ungesättigte Comonomere sind beispielsweise zu nennen Vinylformiat, Vinylacetat, Vinylpropionat, Acrylnitril, N-Vinylcaprolactam, N-Vinylharnstoff, N-Vinylpyrrolidon, C1- bis C6-Alkylvinylether, N-Vinylacetamid, Methyacrylat und Methylmethacrylat.Examples of ethylenically unsaturated comonomers are vinyl formate, vinyl acetate, vinyl propionate, acrylonitrile, N-vinylcaprolactam, N-vinylurea, N-vinylpyrrolidone, C 1 -C 6 -alkyl vinyl ethers, N-vinylacetamide, methyl acrylate and methyl methacrylate.

Bevorzugt werden wässrige Flüssigformulierungen enthaltend 5-25 Gew.-% der Farbstoffzusammensetzung und 1-25 Gew.%, insbesondere 1-15 Gew.-% Poly-N-vinylformamid bezogen auf das Gesamtgewicht der Flüssigformulierung.Preference is given to aqueous liquid formulations comprising 5-25% by weight of the dye composition and 1-25% by weight, in particular 1-15% by weight, of poly-N-vinylformamide, based on the total weight of the liquid formulation.

Die Gew.-% Angaben der Farbstoffe beziehen sich jeweils auf den Farbstoff berechnet in Form seiner freien Säure. Die Farbstoffe liegen in der Flüssigformulierung in Form ihrer Salze vor. Die durch Umsetzung von Direct Yellow 11 erhaltenen Farbstoffe haben bevorzugt als Gegenionen Alkaliionen wie Natrium-, Kalium- und insbesondere Lithiumionen.The percentages by weight of the dyes in each case refer to the dye calculated in the form of its free acid. The dyes are present in the liquid formulation in the form of their salts. The dyes obtained by reacting Direct Yellow 11 preferably have as counterions alkali ions such as sodium, potassium and in particular lithium ions.

Sowohl Direct Yellow 11 als auch Direct Orange 15 sind Stilbenfarbstoffe. Direct Yellow 11 wird als Produkt der Selbstkondensation von 5-Nitro-o-toluolsulfonsäure in wässrig alkalischem Medium erhalten. Seine Umsetzung mit Reduktionsmitteln wie Glucose oder Natriumsulfid führt zu Direct Orange 15 (C.I. 40002 bzw. 40003). Diese Farbstoffe sind Mischungen von Farbstoffen unbestimmter Konstitution. Unter Direct Orange 15 versteht der Fachmann Mischungen, deren Bunttonwinkel nach CIELAB auf gebleichtem Zellstoff sich im Farbraum im Bereich von 45 bis <55 bewegt. Reduziert man Direct Yellow 11 unterstöchiometrisch in bezug auf die Nitrotoluolsulfonsäure, so erhält man Farbstoffgemische mit einem gelborangen Farbton. Man bezeichnet diese bathochrome Verschiebung des Farbtons auch als "Verrötung" von Direct Yellow 11. Eine solche Verrötung des Farbtons lässt sich auch durch thermische Behandlung von Direct Yellow 11 bei einem pH-Wert im Bereich von 12 - 13 erreichen.Both Direct Yellow 11 and Direct Orange 15 are stilbene dyes. Direct Yellow 11 is obtained as a product of the self-condensation of 5-nitro-o-toluenesulfonic acid in an aqueous alkaline medium. Its reaction with reducing agents such as glucose or sodium sulfide leads to Direct Orange 15 (C.I. 40002 or 40003). These dyes are mixtures of dyes of indeterminate constitution. Direct Orange 15 is understood by the person skilled in the art to be mixtures whose hue angle according to CIELAB on bleached pulp varies in the color space in the range from 45 to <55. If direct yellow 11 is reduced substoichiometrically with respect to the nitrotoluenesulfonic acid, dye mixtures having a yellow-orange hue are obtained. This bathochromic shift of hue is also referred to as "reddening" of Direct Yellow 11. Such reddening of hue can also be achieved by thermal treatment of Direct Yellow 11 at a pH in the range of 12-13.

Bevorzugt werden gelborange Farbstoffe, im folgenden auch als teilverrötete Farbstoffe bezeichnet, die erhältlich sind durch Reduktion oder thermische Behandlung von Direct Yellow 11 und deren Bunttonwinkel auf gebleichtem Zellstoff im Farbraum im Bereich von 55 bis 75, insbesondere im Bereich von 55 bis 65, liegt.Yellow-orange dyes, hereinafter also referred to as partially reddened dyes, which are obtainable by reduction or thermal treatment of Direct Yellow 11 and its hue angle on bleached pulp in the color space in the range from 55 to 75, in particular in the range from 55 to 65, are preferred.

Unter blauen Direktfarbstoffen sind direktziehende Farbstoffe mit einem Absorptionsmaximum im Wellenlängenbereich von 560 bis 650 nm zu verstehen. Unter roten Direktfarbstoffen sind direktziehende Farbstoffe mit einem Absorptionsmaximum im Wellenlängenbereich von 490 bis 540 zu verstehen.By direct blue dyes are meant direct dyes having an absorption maximum in the wavelength range from 560 to 650 nm. Red direct dyes are to be understood as meaning direct dyes having an absorption maximum in the wavelength range from 490 to 540.

Bevorzugt werden blaue Direktfarbstoffe wie Direct Violet 9 (C.I. 27855), Direct Violet 35, Direct Violet 51 (C.I. 27905), Direct Blue 86 (C.I. 74180), Direct Blue 199 (C.I. 74190), Direct Blue 218 (C.I. 24401), Direct Blue 267, Direct Blue 273, Direct Blue 279, Direct Blue 281, Direct Blue 71, 273 als Kupferkomplex, und 290. Insbesonders werden Direct Blue 15, 279, 281, 290 und die Farbstoffe der Formeln I, II und III bevorzugt.

Figure imgb0001
Figure imgb0002
Figure imgb0003
 Preferred are blue direct dyes such as Direct Violet 9 (CI 27855), Direct Violet 35, Direct Violet 51 (CI 27905), Direct Blue 86 (CI 74180), Direct Blue 199 (CI 74190), Direct Blue 218 (CI 24401), Direct Blue 267, Direct Blue 273, Direct Blue 279, Direct Blue 281, Direct Blue 71, 273 as a copper complex, and 290. In particular, Direct Blue 15, 279, 281, 290 and the dyes of Formulas I, II and III are preferred.
Figure imgb0001
Figure imgb0002
Figure imgb0003

Ebenfalls bevorzugt werden rote Direktfarbstoffe wie Direct Red 80, Direct Red 81 (C.I. 28160), Direct Red 239, Direct Red 252-255 und Direct Red 262.Also preferred are red direct dyes such as Direct Red 80, Direct Red 81 (C.I. 28160), Direct Red 239, Direct Red 252-255 and Direct Red 262.

Weiterhin kann auch ein brauner Direktfarbstoff, bevorzugt Direct Brown 44, zum Abtönen eingesetzt werden. In der Regel verwendet man in diesem Fall keinen Rotfarbstoff.Furthermore, a brown direct dye, preferably Direct Brown 44, can be used for tinting. As a rule, no red dye is used in this case.

Je nach gewünschtem Braunfarbton ist es möglich, zusätzlich mit einem Orangefarbstoff abzutönen. Beispiele für Orangefarbstoffe sind Direct Orange 15, Direct Orange 34 (C.I. 40215) und Direct Orange 102 (C.I. 29156). In der Regel wird man dies jedoch nicht machen, da mit den teilverröteten Farbstoffen und gegebenenfalls dem roten oder dem braunen Direktfarbstoff sich alle Nuancen erzielen lassen.Depending on the desired brown shade, it is possible to additionally tint with an orange dye. Examples of orange dyes are Direct Orange 15, Direct Orange 34 (C.I. 40215) and Direct Orange 102 (C.I., 29156). In general, however, this will not be done, as can be achieved with the partially reddened dyes and optionally the red or the brown direct dye all nuances.

Bevorzugt werden wässrige Flüssigformulierungen, deren Farbstoffzusammensetzung

40-95 Gew.-%
eines Farbstoffs erhältlich durch Reduktion oder thermische Behandlung von Direct Yellow 11, bevorzugt teilverrötetes Direct Yellow 11,
3-25 Gew.-%
eines blauen Direktfarbstoffes
0-25 Gew.-%
eines roten Direktfarbstoffes und
0-40 Gew.-%
eines braunen Direktfarbstoffes, bevorzugt Direct Brown 44, umfasst.
Preference is given to aqueous liquid formulations whose dye composition
40-95% by weight
a dye obtainable by reduction or thermal treatment of Direct Yellow 11, preferably partially blushed Direct Yellow 11,
3-25% by weight
a blue direct dye
0-25% by weight
a red direct dye and
0-40% by weight
a brown direct dye, preferably Direct Brown 44.

Besonders bevorzugt werden wässrige Flüssigformulierungen, deren Farbstoffzusammensetzung

70-92 Gew.-%
eines Farbstoffs erhältlich durch Reduktion oder thermische Behandlung von Direct Yellow 11, bevorzugt teilverrötetes Direct Yellow 11
5-15 Gew.-%
eines Farbstoffes ausgewählt unter Direct Blue 15, 273, 279, 280, 290 und den Farbstoffen der Formel I, II und III,
3-15 Gew.-%
eines Farbstoffes ausgewählt unter Direct Red 81, 239 ,254 und
0-30 Gew.-%
Direct Brown 44 umfasst.
Particular preference is given to aqueous liquid formulations whose dye composition
70-92% by weight
a dye obtainable by reduction or thermal treatment of Direct Yellow 11, preferably partially blushed Direct Yellow 11
5-15% by weight
a dye selected from Direct Blue 15, 273, 279, 280, 290 and the dyes of the formula I, II and III,
3-15% by weight
a dye selected under Direct Red 81, 239, 254 and
0-30% by weight
Direct Brown 44 includes.

Weiterhin werden wässrige Flüssigformulierungen bevorzugt, deren Farbstoffzusammensetzung

40-80 Gew.-%
eines Farbstoffs erhältlich durch Reduktion oder thermische Behandlung von Direct Yellow 11, bevorzugt teilverrötetes Direct Yellow 11,
5-25 Gew.-%
eines Farbstoffes ausgewählt unter Direct Blue 15, 273, 279, 281, 290 und den Farbstoffen der Formel I, II und III,
15-35 Gew.-%
eines braunen Direktfarbstoffes, bevorzugt Direct Brown 44, umfasst.
Furthermore, aqueous liquid formulations are preferred whose dye composition
40-80% by weight
a dye obtainable by reduction or thermal treatment of Direct Yellow 11, preferably partially blushed Direct Yellow 11,
5-25% by weight
a dye selected from Direct Blue 15, 273, 279, 281, 290 and the dyes of the formula I, II and III,
15-35% by weight
a brown direct dye, preferably Direct Brown 44.

Ebenfalls vorteilhaft sind Flüssigformulierungen, deren Farbstoffzusammensetzung

25-45 Gew.-%
Direct Yellow 11
5-20 Gew.-%
eines Farbstoffes ausgewählt unter Direct Blue 15, 273, 279, 281, 290 und den Farbstoffen der Formel I, II und III
40-60 Gew.-%
eines braunen Direktfarbstoffes bevorzugt Direct Brown 44 enthält.
Also advantageous are liquid formulations, their dye composition
25-45% by weight
Direct Yellow 11
5-20% by weight
a dye selected from Direct Blue 15, 273, 279, 281, 290 and the dyes of the formula I, II and III
40-60% by weight
of a direct brown dye preferably contains Direct Brown 44.

Ferner sind Flüssigformulierungen vorteilhaft, deren Farbstoffzusammensetzung

50-90 Gew.-%
Direct Yellow 11
5-25 Gew.-%
eines Farbstoffes ausgewählt unter Direct Red 81, 239, 254 und
5-25 Gew.-%
eines Farbstoffes ausgewählt unter Direct Blue 15, 273, 279, 281, 290 und den Farbstoffen der Formel I, II und III enthält.
Furthermore, liquid formulations are advantageous, their dye composition
50-90% by weight
Direct Yellow 11
5-25% by weight
a dye selected under Direct Red 81, 239, 254 and
5-25% by weight
a dye selected from Direct Blue 15, 273, 279, 281, 290 and the dyes of the formula I, II and III.

Man erreicht eine Verrötung von Direct Yellow 11 beispielsweise durch seine Umsetzung mit Formaldehyd oder durch basische Kondensation von 5-Nitrotoluolsulfonsäure in Gegenwart von Formaldehyd. Ferner erzielt man eine Verrötung durch Zugabe von Glucose oder Natriumsulfid. Weitere Verrötungsreaktionen sind dem Colour Index und der darin zitierten Literatur zu den Farbstoffen C.I. 40001, 40002, 40003 zu entnehmen.Reddening of Direct Yellow 11 is achieved, for example, by its reaction with formaldehyde or by basic condensation of 5-nitrotoluenesulphonic acid in the presence of formaldehyde. Furthermore, a scorching is achieved by the addition of glucose or sodium sulfide. Further redness reactions are reported in the Color Index and in the literature cited therein C.I. 40001, 40002, 40003.

Bevorzugt werden Farbstoffe, die durch Umsetzung von Direct Yellow 11 mit einem organischen Reduktionsmittel erhalten werden. Organische Reduktionsmittel sind beispielsweise Hydroxyaldehyde wie Pentosen, Hexosen und Heptosen, bevorzugt Glucose.Preference is given to dyes which are obtained by reacting Direct Yellow 11 with an organic reducing agent. Organic reducing agents are, for example, hydroxyaldehydes such as pentoses, hexoses and heptoses, preferably glucose.

Die bevorzugten teilverröteten Farbstoffe sind erhältlich durch unterstöchiometrische Reduktion bezogen auf die Nitrotoluolsulfonsäure.The preferred partially reddened dyes are obtainable by substoichiometric reduction based on the nitrotoluenesulfonic acid.

Besonders bevorzugte teilverrötete Farbstoffe werden erhalten durch Umsetzung von Direct Yellow 11 mit 0,05 bis 0,3 Mol, bevorzugt 0,1 bis 0,25 Mol Hydroxyaldehyd, insbesondere Glucose, pro Mol eingesetzte Nitrotoluolsulfonsäure. Bei Erreichen des gewünschten Farbtons kann die Verrötungsreaktion durch Neutralstellen und Abkühlen gestoppt werden.Particularly preferred partially reddened dyes are obtained by reacting Direct Yellow 11 with 0.05 to 0.3 mol, preferably 0.1 to 0.25 mol, of hydroxyaldehyde, in particular glucose, per mole of nitrotoluenesulfonic acid used. When the desired hue is reached, the reddening reaction can be stopped by neutralizing and cooling.

Die Herstellung von Direct Yellow 11 ist allgemein bekannt. Direct Yellow 11 wird durch Erwärmen einer alkalischen wässrigen Lösung von Nitrotoluolsulfonsäure erhalten. Durch die Umsetzung von Nitrotoluolsulfonsäure mit einem Alkalihydroxid, wie Natrium- oder bevorzugt Lithiumhydroxid, bildet sich zuerst das Salz der Nitrotoluolsulfonsäure, welches im Basischen beim Erwärmen auf 40 - 80°C zum Azostilbenfarbstoff kondensiert.The production of Direct Yellow 11 is well known. Direct Yellow 11 is obtained by heating an alkaline aqueous solution of nitrotoluenesulfonic acid. The reaction of nitrotoluenesulphonic acid with an alkali metal hydroxide, such as sodium hydroxide or, preferably, lithium hydroxide, first forms the salt of nitrotoluenesulphonic acid, which condenses to the azo-styrenic dye in the base when heated to 40.degree.-80.degree.

Bevorzugt setzt man der Mischung vor der Kondensation noch ein wasserlösliches Alkanolamin, in einer Menge von 0,1 bis 0,5 Mol Alkanolamin pro Mol Nitrotoluolsulfonsäure zu. Alkanolamine sind beispielsweise Ethanolamin, Isopropanolamin oder bevorzugt Diethanolamin. Vermutlich wirkt ein solcher Zusatz lösungsvermittelnd auf Reaktionszwischenstufen.Preference is given to adding to the mixture before the condensation nor a water-soluble alkanolamine, in an amount of 0.1 to 0.5 moles of alkanolamine per mole of nitrotoluene sulfonic acid. Alkanolamines are, for example, ethanolamine, isopropanolamine or preferably diethanolamine. Presumably, such an additive acts solubilizing reaction intermediates.

Nach erfolgter Kondensation und Abkühlen wird das alkalische Gemisch annähemd neutral gestellt, beispielsweise mit Essigsäure. Unter Neutralstellen sind im Rahmen dieser Anmeldung pH-Werte im Bereich von 7 bis 9 zu verstehen.After condensation and cooling, the alkaline mixture is made neutral approximately neutral, for example, with acetic acid. For the purposes of this application, neutral points are to be understood as meaning pH values in the range from 7 to 9.

Nach einer bevorzugten Variante setzt man zur Herstellung des teilverröteten oder verröteten Farbstoffs ein Direct Yellow 11 ein, das erhältlich ist durch Umsetzen von 1 Mol Nitrotoluolsulfonsäure mit 1,4 bis 1,8 Mol Lithiumhydroxid, Zugabe von 0,1 bis 0,5 Mol Alkanolamin, Erwärmen des Reaktionsgemisches auf 40 bis 80°C und Neutralstellen.According to a preferred variant, a direct yellow 11 is used to prepare the partially reddened or reddened dyestuff, which is obtainable by reacting 1 mol of nitrotoluenesulphonic acid with 1.4 to 1.8 mol of lithium hydroxide, adding from 0.1 to 0.5 mol of alkanolamine , Heating the reaction mixture to 40 to 80 ° C and neutral.

Nach einer besonders bevorzugten Variante werden die Herstellung von Direct Yellow 11 und der Verrötungsschritt ohne Zwischenisolierung von Direct Yellow 11 durchgeführt. Der teilverrötete Farbstoff ist dann direkt erhältlich durch Umsetzung von 1 Mol Nitrotoluolsulfonsäure mit 1,4 bis 1,8 Mol Lithiumhydroxid, Zugabe von 0,1 bis 0,5 Mol Alkanolamin, Erwärmen des Reaktionsgemisches auf 40 bis 80°C, Umsetzen mit 0,05 bis 0,3 Mol Glucose bezogen auf ein Mol eingesetzte Nitrotoluolsulfonsäure und Neutralstellen.According to a particularly preferred variant, the preparation of Direct Yellow 11 and the Verrötungsschritt be carried out without intermediate isolation of Direct Yellow 11. The partially reddened dye is then directly obtainable by reacting 1 mol of nitrotoluenesulfonic acid with 1.4 to 1.8 mol of lithium hydroxide, adding 0.1 to 0.5 mol of alkanolamine, heating the reaction mixture to 40 to 80 ° C, reacting with 0, 05 to 0.3 moles of glucose based on one mole of nitrotoluenesulfonic acid used and neutral points.

Besonders bevorzugt ist eine Arbeitsweise, bei der man während der Kupplung und Reduktion die Temperatur kontinuierlich, in linearer oder nichtlinearer Weise, oder periodisch erhöht. Die Temperaturdifferenz zwischen dem Beginn der Kupplung und dem Ende der Reduktion kann bis zu 40 K betragen. Im Allgemeinen beträgt diese Differenz 15 bis 25 K.Particularly preferred is a procedure in which during the coupling and reduction, the temperature is increased continuously, in a linear or non-linear manner, or periodically. The temperature difference between the beginning of the coupling and the end of the reduction can be up to 40 K. In general, this difference is 15 to 25 K.

Bevorzugt werden wässrige Flüssigformulierungen, die Polyvinylformamid in Kombination mit Harnstoff enthalten. Bevorzugt werden wässrige Flüssigformulierungen umfassend 5-25 Gew.-% Farbstoffzusammensetzung, 1-25 Gew.-% bevorzugt 1-15 Gew.-% Poly-N-vinylformamid und 1-30 Gew.-% Harnstoff, bezogen auf das Gesamtgewicht der wässrigen Flüssigformulierung, wobei die Gesamtmenge aus Poly-N-vinylformamid und Harnstoff 40 Gew.-% nicht übersteigt.Preference is given to aqueous liquid formulations which contain polyvinylformamide in combination with urea. Preference is given to aqueous liquid formulations comprising 5-25% by weight of dye composition, 1-25% by weight, preferably 1-15% by weight of poly-N-vinylformamide and 1-30% by weight of urea, based on the total weight of the aqueous Liquid formulation wherein the total amount of poly-N-vinylformamide and urea does not exceed 40% by weight.

Dabei werden Mischungen bevorzugt, in denen die Summe aus den beiden Komponenten 10-25 Gew.% beträgt. Das bedeutet, bei geringem Polyvinylformamidgehalt im Bereich von 1 - 5 Gew.-% werden hohe Harnstoffgehalte im Bereich von >9-24 Gew.-% bevorzugt. Werden nur 1-9 Gew.-% Harnstoff zugesetzt, so beträgt der bevorzugte Anteil Polyvinylformamid >5 -16 Gew.-%.Mixtures are preferred in which the sum of the two components is 10-25% by weight. That is, at low Polyvinylformamidgehalt in the range of 1 - 5 wt .-%, high urea contents in the range of> 9-24 wt .-% are preferred. If only 1-9% by weight of urea is added, the preferred proportion of polyvinylformamide is> 5-16% by weight.

Bevorzugt werden wässrige Flüssigformulierungen umfassend 10-25 Gew.-% Farbstoffzusammensetzung, 1-15 Gew.-% Poly-N-vinylformamid und 1-30 Gew.-% Harnstoff. Besonders bevorzugt werden wässrige Flüssigformulierungen umfassend 15-20 Gew.-% Farbstoffzusammensetzung speziell die bevorzugten Farbstoffzusammensetzungen, 1-10 Gew.-% Poly-N-vinylformamid und 1-20 Gew.% Harnstoff.Preference is given to aqueous liquid formulations comprising 10-25% by weight of dye composition, 1-15% by weight of poly-N-vinylformamide and 1-30% by weight of urea. Particular preference is given to aqueous liquid formulations comprising 15-20% by weight of dye composition, especially the preferred dye compositions, 1-10% by weight of poly-N-vinylformamide and 1-20% by weight of urea.

Synthesebedingt enthalten die bevorzugten Flüssigformulierungen noch Diethanolamin. Daher werden Flüssigformulierungen umfassend 5-25 Gew.-% Farbstoffzusammensetzung, 1-15 Gew.-%, bevorzugt 1-10 Gew.% Poly-N-vinylformamid, 0,5-5 Gew.-%, bevorzugt 1,5-3 Gew.-% eines Alkanolamins und 1-30 Gew.-%, bevorzugt 1-25 Gew.%, Harnstoff bevorzugt.Due to the synthesis, the preferred liquid formulations still contain diethanolamine. Therefore, liquid formulations comprising 5-25% by weight of the dye composition, 1-15% by weight, preferably 1-10% by weight of poly-N-vinylformamide, 0.5-5% by weight, preferably 1.5-3% by weight of an alkanolamine and 1-30% by weight. %, preferably 1-25 wt.%, Urea preferred.

Die Farbstoffe können als feuchter Presskuchen oder auch in getrockneter Form eingesetzt werden. In diesem Fall stellt man eine Lösung her, indem man das Poly-N-vinylformamid und den Harnstoff zusetzt. Bevorzugt setzt man direkt das Reaktionsgemisch der Verrötungsreaktion von Direct Yellow 11 ohne zusätzlichen Isolierungsschritte ein. Bevorzugt setzt man zuerst den Harnstoff der erhaltenen Reaktionsmischung der Verrötungsreaktion von Direct Yellow 11 zu. Anschließend werden dann das Poly-N-vinylformamid und gegebenenfalls die weiteren Farbstoffe zugesetzt.The dyes can be used as a moist presscake or in a dried form. In this case, a solution is prepared by adding the poly-N-vinylformamide and the urea. Preference is given to directly using the reaction mixture of the reddening reaction of Direct Yellow 11 without additional isolation steps. Preferably, the urea of the reaction mixture obtained is first added to the reddening reaction of Direct Yellow 11. Subsequently, the poly-N-vinylformamide and optionally the further dyes are added.

Weitere Zusätze in der Flüssigformulierung können prinzipiell sein C1-C4-Alkanole, z.B. Methanol, Ethanol, Propanol, Isopropanol, Butanol, Isobutanol, sec-Butanol oder tert-Butanol, Carbonsäureamide, wie N,N-Dimethylformamid oder N,N-Dimethylacetamid, Ketone oder Ketoalkohole, wie Aceton, Methylethylketon oder 2-Methyl-2-hydroxypentan-4-on, Mono-, Oligo- oder Polyalkylenglykole oder -thioglykole, die C2-C6-Alkyleneinheiten aufweisen, wie Ethylenglykol, 1,2- oder 1,3-Propylenglykol, 1,2- oder 1,4-Butylenglykol, Hexan-1,6-diol, Diethylenglykol, Triethylenglykol, Dipropylenglykol, Thiodiglykol, Polyethylenglykol oder Polypropylenglykol, andere Polyole, wie Glycerin oder Hexan-1,2,6-triol, C1-C4-Alkylether von mehrwertigen Alkoholen, wie Ethylenglykolmonomethyl- oder -monoethylether, Diethylenglykolmonomethyl- oder - monoethylether, Diethylenglykolmonobutylether (Butyldiglykol) oder Triethylenglykolmonomethyl- oder-monoethylether, C1-C4-Alkylester von mehrwertigen Alkoholen, γ-Butyrolacton oder Dimethylsulfoxid. Geeignete solubilisierende Zusätze sind ferner Lactame, wie ε-Caprolactam, Pyrrolidin-2-on oder N-Methylpyrrolidin-2-on, cyclische Harnstoffe, wie 1,3-Dimethylimidazolidin-2-on oder 1,3-Dimethylhexahydropyrimid-2-on sowie Polyacrylsäuren, Polyacrylsäurederivate, Polyvinylacetate, Polyvinylalkohole, Polyvinylpyrrolidone, Polysiloxane oder Copolymere der jeweiligen Monomere. Desgleichen können Oligomere des Ethylenoxids oder Propylenoxids oder Derivate dieser Oligomere zur Anwendung kommen.Other additives in the liquid formulation may in principle be C 1 -C 4 -alkanols, for example methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol or tert-butanol, carboxamides, such as N, N-dimethylformamide or N, N Dimethylacetamide, ketones or ketoalcohols such as acetone, methyl ethyl ketone or 2-methyl-2-hydroxypentan-4-one, mono-, oligo- or polyalkylene glycols or thioglycols having C 2 -C 6 -alkylene units such as ethylene glycol, 1,2 or 1,3-propylene glycol, 1,2- or 1,4-butylene glycol, hexane-1,6-diol, diethylene glycol, triethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol or polypropylene glycol, other polyols, such as glycerol or hexane-1,2 , 6-triol, C 1 -C 4 alkyl ethers of polyhydric alcohols, such as ethylene glycol monomethyl or monoethyl ether, diethylene glycol monomethyl or - monoethyl ether, diethylene glycol monobutyl ether (butyl diglycol) or triethylene glycol monomethyl or monoethyl ether, C 1 -C 4 alkyl esters of polyhydric alcohol en, γ-butyrolactone or dimethyl sulfoxide. Suitable solubilizing additives are also lactams, such as ε-caprolactam, pyrrolidin-2-one or N-methylpyrrolidin-2-one, cyclic ureas, such as 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimid-2-one and Polyacrylic acids, polyacrylic acid derivatives, polyvinyl acetates, polyvinyl alcohols, polyvinylpyrrolidones, polysiloxanes or copolymers of the respective monomers. Likewise, oligomers of ethylene oxide or propylene oxide or derivatives of these oligomers may be used.

Diese Zusätze können der Flüssigformulierung zugefügt werden, zeigen jedoch keinen nennenswerten Effekt. Ihr Anteil wird daher in der Regel 10 Gew.-%, bezogen auf das Gesamtgewicht der Flüssigformulierung, nicht überschreiten und beträgt häufig nicht mehr als 5 Gew.%. Nach einer bevorzugten Ausführungsform enthalten die erfindungsgemäßen Flüssigformulierungen keine (d.h. <1 Gew.%) derartigen Zusätze. Nach einer anderen bevorzugten Ausführungsform enthalten Flüssigformulierungen mit Direct Brown 44 zusätzlich bis zu 5 Gew.-% Polyethylenglykol als Zusatz.These additives can be added to the liquid formulation, but have no appreciable effect. Their proportion will therefore usually not exceed 10 wt .-%, based on the total weight of the liquid formulation, and is often not more than 5 wt.%. In a preferred embodiment, the liquid formulations of the present invention contain no (i.e., <1% by weight) such additives. According to another preferred embodiment, liquid formulations with Direct Brown 44 additionally contain up to 5% by weight of polyethylene glycol as additive.

Die erhaltenen Lösungen weisen hervorragende Lagerstabilität auf. Sie ergeben gute Papierfärbung insbesondere in der Masse.The solutions obtained have excellent storage stability. They give good paper coloration especially in the mass.

Die nachfolgenden Beispiele sollen die Erfindung näher erläutern.The following examples are intended to explain the invention in more detail.

a) Herstellung von verrötetem Direct Yellow 11a) Preparation of reddened Direct Yellow 11

Es wurden 1,54 l Wasser vorgelegt und anschließend 1,10 kg p-Nitrotoluolsulfonsäure (83 gew.-%ig, 4,21 Mol) eingetragen. Es wurden insgesamt 300 g festes Lithiumhydroxid (56 gew.-%ig, 7 Mol) portionsweise zugesetzt. Anschließend gab man 110 g Diethanolamin zu und rührte 15 h bei 55 °C. Es folgte die Zugabe von einem Liter Wasser. Man rührte für 10 min, setzte 125 g Glucosemonohydrat zu und erwärmte für 2 h auf eine Temperatur von 65 °C. Anschließend wurde mit 50 g Eisessig ein pH-Wert von 9,0 eingestellt. Das Produkt wurde als braun-rote gelartige Substanz erhalten. Es wurden 4,19 kg Produkt erhalten mit einem Farbstoffgehalt von 26,2 %.There were submitted to 1.54 liters of water and (% strength by weight, 4.21 mol of 83 .-) was added followed by 1.10 kg p -Nitrotoluolsulfonsäure. A total of 300 grams of solid lithium hydroxide (56 wt%, 7 moles) was added portionwise. Subsequently, 110 g of diethanolamine were added and stirred for 15 h at 55 ° C. This was followed by the addition of one liter of water. The mixture was stirred for 10 minutes, added 125 g of glucose monohydrate and heated for 2 h to a temperature of 65 ° C. Subsequently, a pH of 9.0 was adjusted with 50 g of glacial acetic acid. The product was obtained as a brown-red gel-like substance. There were 4.19 kg of product obtained with a dye content of 26.2%.

b) Herstellung von Direct Yellow 11b) Preparation of Direct Yellow 11

Es wurden 1,54 l Wasser vorgelegt und anschließend 1,10 kg p-Nitrotoluolsulfonsäure (83 gew.-%ig, 4,21 Mol) eingetragen. Es wurden insgesamt 270 g festes Lithiumhydroxid (56 gew.%ig, 7 Mol) portionsweise zugesetzt. Anschließend gab man 83 g Diethanolamin zu und rührte 15 h bei 55 °C. Es folgte die Zugabe von 1,7 Liter Wasser. Man erwärmte für 2 h auf eine Temperatur von 65 °C. Anschließend wurde mit 70 g Eisessig ein pH-Wert von 9,0 eingestellt. Das Produkt wurde als braun-rote gelartige Substanz erhalten. Es wurden 4,75 kg Produkt erhalten mit einem Farbstoffgehalt von 25,0 %.1.54 l of water were initially charged and then 1.10 kg of p- nitrotoluenesulphonic acid (83% strength by weight, 4.21 mol) were introduced. A total of 270 grams of solid lithium hydroxide (56 wt%, 7 moles) was added portionwise. Then, 83 g of diethanolamine were added and stirred for 15 h at 55 ° C. This was followed by the addition of 1.7 liters of water. The mixture was heated for 2 h to a temperature of 65 ° C. Subsequently, a pH of 9.0 was set with 70 g of glacial acetic acid. The product was obtained as a brown-red gel-like substance. There were obtained 4.75 kg of product with a dye content of 25.0%.

c) Test auf Lagerstabilitätc) Storage stability test

Die verschlossenen Proben wurden jeweils 8 Wochen bei 4°C und 50°C parallel gelagert und anschließend optisch nach folgendem Schlüssel bewertet:
1 = Probe läuft klar ab, keine Rückstände; 1-2 = Probe läuft klar ab, nur sehr wenig Rückst. sichtbar; 2 = Probe läuft nicht klar ab, bzw. zeigt merklichen Bodensatz oder Wandbelag; 2-3 = deutlicher Bodensatz, starker Wandbelag; 3 = viel Bodensatz, starker Wandbelag oder Probe wird fest oder geliert.The sealed samples were each stored in parallel at 4 ° C. and 50 ° C. for 8 weeks and then evaluated optically according to the following key:
1 = sample runs clear, no residue; 1-2 = sample is clear, only very little residue. visible, noticeable; 2 = sample does not clear, or shows noticeable sediment or wall covering; 2-3 = significant sediment, strong wall covering; 3 = much sediment, strong wall covering or sample is solidified or gelled.

d) Herstellung der Flüssigformulierungd) Preparation of the liquid formulation Beispiel 1example 1

25,7 g des nach a) erhaltenen verröteten Direktgelb 11, 4,8 g Poly-N-vinylformamid mit einem mittleren Molekulargewicht von 1500, 1,0 g Direct Rot 81 in Form einer konzentrierten wässrigen Lösung des Triethanolammoniumsalzes, 1,0 g Direct Blue 281 in Form einer konzentrierten wässrigen Lösung des gemischten Natrium/Lithiumsalzes sowie 17,9 g Wasser wurden zusammengegeben und 10 min intensiv gerührt. Anschließend wurde die Probe in ein 50 ml Schraubdeckelglas gefüllt und in dieser Form bei der entsprechenden Temperatur für 8 Wochen gelagert. Diese Probe wurde nach 8 Wochen sowohl bei 4°C mit 1-2 und bei 50°C mit 1-2 bewertet.25.7 g of reddened direct yellow 11 obtained according to a), 4.8 g of poly-N-vinylformamide having an average molecular weight of 1500, 1.0 g of Direct Red 81 in the form of a concentrated aqueous solution of the triethanolammonium salt, 1.0 g of direct Blue 281 in the form of a concentrated aqueous solution of the mixed sodium / lithium salt and 17.9 g of water were combined and stirred vigorously for 10 min. Subsequently The sample was filled into a 50 ml screw-top jar and stored in this form at the appropriate temperature for 8 weeks. This sample was scored after 1-2 weeks at 1-2 ° C at 4 ° C and 1-2 at 50 ° C.

Analog zu Beispiel 1 wurden Flüssigformulierungen mit der Tabelle 1 zu entnehmenden Zusammensetzungen hergestellt. Tabelle 2 gibt die gewählten Farbstoffzusammensetzungen wieder. Als Gelbfarbstoff wurde in den Beispielen 1-9 und den Vergleichsbeispielen V1 und V2 das nach a) hergestellte verrötete Direct Yellow 11 (Farbstoffgehalt 26,2 Gew.-%) eingesetzt und in den Beispielen 10, 11 und V3 das nach b) hergestellte nicht verrötete Direkt Yellow 11 (Farbstoffgehalt 25,0 % eingesetzt. Tabelle 1 Bsp. Harnstoff Polyvinylformamid* H2O Farbstoffzus. Stabilität n. 8 Wochen [g] [%] [g] [%] [g] [g] [%] 4°C 50°C 1 0,0 0 4,8 8 17,9 8,8 14 1-2 1-2 2 0,0 0 4,6 5 17,0 18,3 18 1-2 1-2 3 0,0 0 25,0 10 92,5 34,7 14 1 1-2 4 4,6 5 4,6 5 12,4 18,3 18 1-2 1-2 5 25,0 10 25,0 10 67,5 34,7 14 1-2 1-2 6 4,2 14 0,2 1 5,9 4,9 16 1 1-2 7 4,2 14 0,4 1 5,7 4,9 16 1-2 1 8 9,2 9 0,9 1 11,5 18,3 18 1-2 1-2 9 50,0 20 5,0 2 62,5 34,7 14 1 1-2 10 9,2 9 0,9 1 11,0 18,1 18 1 (6W) 2 (6W) 11 9,2 9 0,5 1 11,5 18,1 18 1-2 (6W) 1-2 (6W) V1 21,2 21 0,0 0 15,0 16,7 17 1-2# 2# V2 22,5 22 0,0 0 15,8 16,2 16 1-2 2-3 V3 11,2 11 0,0 0 7,8 18,6 19 3 (4W) 3 (4W) # Belag * Es wurde ein Polyvinylformamid mit einem mittleren Molekulargewicht von 1500 eingesetzt. Tabelle 2 Bsp, Gelb-Farbstoff Rot/Braun-Farbstoff ** Blau-Farbstoff *** Summe Farbs. [g]1) [g]2). [%]* Typ [g] [%]* Typ [g] [%]* [g] 1 25,7 6,7 77 D.R.81 1,0 12 D.B.281 1,0 12 8,8 2 24,3 6,4 35 D.Bn.44 9,2 50 D.B.279 2,8 15 18,3 3 132,5 34,7 100 - 0,0 0 - 0,0 0 34,7 4 24,3 6,4 35 D.Bn.44 9,2 50 D.B.279 2,8 15 18,3 5 132,5 34,7 100 - 0,0 0 - 0,0 0 34,7 6 10,7 2,8 57 DBn.44 1,3 27 D.B.279 0,8 15 4,9 7 10,7 2,8 57 D.Bn.44 1,3 27 D.B.279 0,8 15 4,9 8 24,3 6,4 35 D.Bn.44 9,2 50 D.B.279 2,8 15 18,3 9 132,5 34,7 100 - 0,0 0 - 0,0 0 34,7 10 24,7 6,2 34 D.Bn.44 9,2 51 D.B.279 2,8 15 18,4 11 24,7 6,2 34 D.Bn.44 9,2 51 D.B.279 2,8 15 18,4 V1 51,2 13,4 80 D.R. 239 0,8 5 D.B.279 2,4 14 16,7 V2 54,1 14,2 88 D.R.81 0,2 1 D.B.279 1,8 11 16,2 V3 26,8 6,7 36 D.Bn.44 9,2 49 D.B.279 2,8 15 19,0 1) Farbstoffeinwaage des Produktes der Gelbsynthese nach a) bzw. b) 2) umgerechnet auf den Farbstoffanteil in Gramm * umgerechnet auf den Farbstoffanteil in Prozent ** angegeben sind die Menge Farbsäure. D.R. 239 wird als konzentrierte, wässrige Lösung des gemischten Natrium/Ethanolammoniumsalzes zugegeben, D.R. 81 als konzentrierte wässrige Lösung des Triethanolammoniumsalzes, D.Bn. 44 als konzentrierte wässrige Lösung des gemischten Natrium/Ammoniumsalzes *** angegeben sind die Menge Farbsäure, D.B. 279 wird als konzentrierte wässrige Lösung des Triethanolammoniumsalzes, D.B 281 als konzentrierte wässrige Lösung des gemischten Natrium/Lithiumsalzes zugegeben. Analogous to Example 1, liquid formulations with compositions to be taken from Table 1 were prepared. Table 2 represents the selected dye compositions. The yellow dye used in Examples 1-9 and Comparative Examples V1 and V2 was the reddish Direct Yellow 11 (dye content 26.2% by weight) prepared according to a) and the one prepared according to b) in Examples 10, 11 and V3 Reddened Direct Yellow 11 (dye content 25.0% used. Table 1 Ex. urea Polyvinylformamide * H 2 O Farbstoffzus. Stability n. 8 weeks [G] [%] [G] [%] [G] [G] [%] 4 ° C 50 ° C 1 0.0 0 4.8 8th 17.9 8.8 14 1-2 1-2 2 0.0 0 4.6 5 17.0 18.3 18 1-2 1-2 3 0.0 0 25.0 10 92.5 34.7 14 1 1-2 4 4.6 5 4.6 5 12.4 18.3 18 1-2 1-2 5 25.0 10 25.0 10 67.5 34.7 14 1-2 1-2 6 4.2 14 0.2 1 5.9 4.9 16 1 1-2 7 4.2 14 0.4 1 5.7 4.9 16 1-2 1 8th 9.2 9 0.9 1 11.5 18.3 18 1-2 1-2 9 50.0 20 5.0 2 62.5 34.7 14 1 1-2 10 9.2 9 0.9 1 11.0 18.1 18 1 (6W) 2 (6W) 11 9.2 9 0.5 1 11.5 18.1 18 1-2 (6W) 1-2 (6W) V1 21.2 21 0.0 0 15.0 16.7 17 1-2 # 2 # V2 22.5 22 0.0 0 15.8 16.2 16 1-2 2-3 V3 11.2 11 0.0 0 7.8 18.6 19 3 (4W) 3 (4W) # Topping * A polyvinylformamide with an average molecular weight of 1500 was used. Ex, Yellow dye Red / brown dye ** Blue dye *** Sum of colors. [g] 1) [g] 2) . [%] * Type [G] [%] * Type [G] [%] * [G] 1 25.7 6.7 77 DR81 1.0 12 DB281 1.0 12 8.8 2 24.3 6.4 35 D.Bn.44 9.2 50 DB279 2.8 15 18.3 3 132.5 34.7 100 - 0.0 0 - 0.0 0 34.7 4 24.3 6.4 35 D.Bn.44 9.2 50 DB279 2.8 15 18.3 5 132.5 34.7 100 - 0.0 0 - 0.0 0 34.7 6 10.7 2.8 57 DBn.44 1.3 27 DB279 0.8 15 4.9 7 10.7 2.8 57 D.Bn.44 1.3 27 DB279 0.8 15 4.9 8th 24.3 6.4 35 D.Bn.44 9.2 50 DB279 2.8 15 18.3 9 132.5 34.7 100 - 0.0 0 - 0.0 0 34.7 10 24.7 6.2 34 D.Bn.44 9.2 51 DB279 2.8 15 18.4 11 24.7 6.2 34 D.Bn.44 9.2 51 DB279 2.8 15 18.4 V1 51.2 13.4 80 DR 239 0.8 5 DB279 2.4 14 16.7 V2 54.1 14.2 88 DR81 0.2 1 DB279 1.8 11 16.2 V3 26.8 6.7 36 D.Bn.44 9.2 49 DB279 2.8 15 19.0 1) Dye balance of the product of the yellow synthesis according to a) or b) 2) converted to the dye content in grams * converted to the dye content in percent ** indicated are the amount of colored acid. DR 239 is added as a concentrated aqueous solution of the mixed sodium / ethanolammonium salt, DR 81 as a concentrated aqueous solution of the triethanolammonium salt, D.Bn. 44 as a concentrated aqueous solution of the mixed sodium / ammonium salt the amount of colored acid is given, DB 279 is added as a concentrated aqueous solution of the triethanolammonium salt, DB 281 as a concentrated aqueous solution of the mixed sodium / lithium salt.

Claims (9)

Wässrige Flüssigformulierung enthaltend 5-25 Gew.-% einer Farbstoffzusammensetzung umfassend 20-100 Gew.% Direct Yellow 11 oder eines Farbstoffs erhältlich durch Reduktion oder thermische Behandlung von Direct Yellow 11 0-30 Gew.% eines blauen Direktfarbstoffes, 0-30 Gew.-% eines roten Direktfarbstoffes und 0-60 Gew.-% eines braunen Direktfarbstoffes jeweils bezogen auf die Farbstoffzusammensetzung und 1-25 Gew.-% Poly-N-vinylformamid und/oder eines Polymers, das erhalten wird durch Polymerisation einer Mischung aus einem oder mehreren ethylenisch ungesättigten Monomere und > 50 Gew.-% N-Vinylformamid bezogen auf die Gesamtmonomere, bezogen auf das Gesamtgewicht der wässrigen Flüssigformulierung.Aqueous liquid formulation containing Comprising 5-25% by weight of a dye composition 20-100% by weight of Direct Yellow 11 or a dye obtainable by reduction or thermal treatment of Direct Yellow 11 0-30% by weight of a blue direct dye, 0-30 wt .-% of a red direct dye and 0-60 wt .-% of a brown direct dye in each case based on the dye composition and 1-25% by weight of poly-N-vinylformamide and / or of a polymer obtained by polymerization of a mixture of one or more ethylenically unsaturated monomers and> 50% by weight of N-vinylformamide based on the total monomers, based on the total weight of the aqueous liquid formulation. Wässrige Flüssigformulierung nach Anspruch 1 enthaltend 5-25 Gew.-% einer Farbstoffzusammensetzung und 1-25 Gew.% Poly-N-vinylformamid bezogen auf das Gesamtgewicht der wässrigen Flüssigformulierung.An aqueous liquid formulation according to claim 1 comprising 5-25% by weight of a dye composition and 1-25% by weight of poly-N-vinylformamide based on the total weight of the aqueous liquid formulation. Wässrige Flüssigformulierung nach einem der Ansprüche 1 bis 2, deren Farbstoffzusammensetzung 40-95 Gew.-% eines Farbstoffs erhältlich durch Reduktion oder thermische Behandlung von Direct Yellow 11, 3-25 Gew.-% eines blauen Direktfarbstoffes 0-25 Gew.-% eines roten Direktfarbstoffes und 0-40 Gew.-% eines braunen Direktfarbstoffes, bevorzugt Direct Brown 44, umfasst. Aqueous liquid formulation according to any one of claims 1 to 2, the dye composition thereof 40-95% by weight of a dye obtainable by reduction or thermal treatment of Direct Yellow 11, 3-25% by weight of a blue direct dye 0-25 wt .-% of a red direct dye and 0-40 wt .-% of a brown direct dye, preferably Direct Brown 44 comprises. Wässrige Flüssigformulierung nach einem der Ansprüche 1 bis 2, deren Farbstoffzusammensetzung 25-45 Gew.-% Direct Yellow 11 5-20 Gew.-% eines Farbstoffes ausgewählt unter Direct Blue 15, 273, 279, 281, 290 und den Farbstoffen der Formel I, II und III 40-60 Gew.-% eines braunen Direktfarbstoffes enthält. Aqueous liquid formulation according to any one of claims 1 to 2, the dye composition thereof 25-45% by weight of Direct Yellow 11 5-20 wt .-% of a dye selected from Direct Blue 15, 273, 279, 281, 290 and the dyes of the formula I, II and III Contains 40-60 wt .-% of a brown direct dye. Wässrige Flüssigformulierung nach einem der Ansprüche 1 bis 2, deren Farbstoffzusammensetzung 50-90 Gew.-% Direct Yellow 11 5-25 Gew.-% eines Farbstoffes ausgewählt unter Direct Red 81, 239, 254 und 5-25 Gew.-% eines Farbstoffes ausgewählt unter Direct Blue 15, 273, 279, 281, 290 und den Farbstoffen der Formel I, II und III enthält. Aqueous liquid formulation according to any one of claims 1 to 2, the dye composition thereof 50-90% by weight of Direct Yellow 11 5-25% by weight of a dye selected from Direct Red 81, 239, 254 and 5-25 wt .-% of a dye selected from Direct Blue 15, 273, 279, 281, 290 and the dyes of the formula I, II and III. Wässrige Flüssigformulierung nach einem der Ansprüche 1 bis 3, deren Farbstoffzusammensetzung einen Farbstoff umfasst, der erhältlich ist durch Umsetzung von Direct Yellow 11 mit einem organischen Reduktionsmittel.An aqueous liquid formulation according to any one of claims 1 to 3, the dye composition of which comprises a dye obtainable by reacting Direct Yellow 11 with an organic reducing agent. Wässrige Flüssigformulierung nach einem der Ansprüche 1 bis 6 umfassend 5-25 Gew.-% Farbstoffzusammensetzung 1-25 Gew.-% Poly-N-vinylformamid und 1-30 Gew.-% Harnstoff bezogen auf das Gesamtgewicht der wässrigen Flüssigformulierung, wobei die Gesamtmenge aus Poly-N-vinylformamid und Harnstoff 40 Gew.-% nicht übersteigt.An aqueous liquid formulation according to any one of claims 1 to 6 comprising 5-25% by weight of the dye composition 1-25 wt .-% poly-N-vinylformamide and 1-30% by weight of urea based on the total weight of the aqueous liquid formulation, wherein the total amount of poly-N-vinylformamide and urea does not exceed 40% by weight. Wässrige Flüssigformulierung nach einem der Ansprüche 1 bis 7 umfassend 5-25 Gew.-% Farbstoffzusammensetzung 1-10 Gew.-% Poly-N-vinylformamid 0,5-5 Gew.-% Alkanolamin und 1-25 Gew.-% Harnstoff. An aqueous liquid formulation according to any one of claims 1 to 7 comprising 5-25% by weight of the dye composition 1-10% by weight of poly-N-vinylformamide 0.5-5 wt .-% alkanolamine and 1-25% by weight of urea. Verwendung der wässrigen Flüssigformulierung gemäß den Ansprüchen 1 bis 8 zum Färben von Papier und Karton.Use of the aqueous liquid formulation according to claims 1 to 8 for dyeing paper and cardboard.
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WO2007057370A2 (en) * 2005-11-18 2007-05-24 Basf Se Liquid direct dye formulations

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WO2007057370A2 (en) * 2005-11-18 2007-05-24 Basf Se Liquid direct dye formulations
WO2007057370A3 (en) * 2005-11-18 2007-08-09 Basf Ag Liquid direct dye formulations
US7713311B2 (en) 2005-11-18 2010-05-11 Basf Aktiengesellschaft Liquid direct dye formulations

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